1. Field of the Invention
This invention relates to the hydroconversion of heavy hydrocarbon oils. More particularly, it relates to a hydrotreating catalyst system with improved cumulative pore volume properties and to processes for producing and using such material.
2. Description of Related Information
In petroleum refining there is frequently a need to convert high boiling fractions of petroleum distillates, such as vacuum resid, to lower boiling fractions which are of higher value and more readily handleable and/or marketable. The following patents illustrate various ways of dealing with this need.
U.S. Pat. No. 4,579,646 discloses a bottoms visbreaking hydroconversion process wherein hydrocarbon charge is partially coked, and the coke is contacted within the charge stock with an oil-soluble metal compound of a metal of Group IV-B, V-B, VII-B, or VIII to yield a hydroconversion catalyst.
U.S. Pat. No. 4,226,742 discloses catalyst for the hydroconversion of heavy hydrocarbon oils formed in situ from oil-soluble metal compound by heating in the presence of hydrogen. Oil soluble metal compound is added in amounts 10-950 ppm, preferably 50-200, to feedstock. This mixture is converted to a solid, noncolloidal form by heating the mixture at 325.degree.-415.degree. C. in the presence of hydrogen gas. Hydroconversion is effected at 26.degree.-482.degree. C. and then the catalytic solids are separated from the hydroconversion effluent.
U.S. Pat. No. 4,178,227 discloses upgrading heavy carbonaceous feeds by slurry hydroconversion and fluid coking gasification, using as catalyst which is an in situ-formed metal compound, and with recycled solid fines.
U.S. Pat. No. 4,724,069 discloses hydrofining in the presence of a supported catalyst bearing a VI-B, VII-B, or VIII metal on alumina, silica, or silica-alumina. There is introduced with the charge oil, as additive, a naphthenate of Co or Fe.
U.S. Pat. No. 4,567,156 discloses hydroconversion in the presence of a chromium catalyst prepared by adding a water-soluble aliphatic polyhydroxy compound (such as glycerol) to an aqueous solution of chromic acid, adding a hydrocarbon thereto, and heating the mixture in the presence of hydrogen sulfide to yield a slurry.
U.S. Pat. No. 4,564,441 discloses hydrofining in the presence of a decomposable compound of a metal (Cu, Zn, III-B, IV-B, VI-B, VII-B, or VIII) mixed with a hydrocarbon-containing feed stream; and the mixture is then contacted with a "suitable refractory inorganic material" such as alumina.
U.S. Pat. No. 4,557,823 discloses hydrofining in the presence of a decomposable compound of a IV-B metal and a supported catalyst containing a metal of VI-B, VII-B, or VIII.
U.S. Pat. No. 4,557,824 discloses demetallization in the presence of a decomposable compound of a VI-B, VII-B, or VIII metal admitted with the charge and a heterogeneous catalyst containing a phosphate of Zr, Co, or Fe.
U.S. Pat. No. 4,551,230 discloses demetallization in the presence of a decomposable compound of a IV-B, V-B, VI-B, VII-B, or VIII metal admitted with the charge and a heterogeneous catalyst containing NiAs.sub.x on alumina.
U.S. Pat. No. 4,430,207 discloses demetallization in the presence of a decomposable compound of a V-B, VI-B, VII-B, or VIII metal admitted with the charge and a heterogeneous catalyst containing a phosphate of Zr or Cr.
U.S. Pat. No. 4,389,301 discloses hydroprocessing in the presence of added dispersed hydrogenation catalyst (typically ammonium molybdate) and added porous contact particles (typically FCC catalyst fines, alumina, or naturally occurring clay).
U.S. Pat. No. 4,352,729 discloses hydrotreating in the presence of a molybdenum blue solution in polar organic solvent introduced with the hydrocarbon charge.
U.S. Pat. No. 4,338,183 discloses liquefaction of coal in the presence of unsupported finely divided metal catalyst.
U.S. Pat. No. 4,298,454 discloses hydroconversion of a coal-oil mixture in the presence of a thermally decomposable compound of a IV-B, V-B, VI-B VII-B, or VIII metal, preferably Mo.
U.S. Pat. No. 4,134,825 discloses hydroconversion of heavy hydrocarbons in the presence of an oil-soluble compound of IV-B, V-B, VI-B, VII-B, or VIII metal added to charge, the compound being converted to solid, non-colloidal form by heating in the presence of hydrogen.
U.S. Pat. No. 4,125,455 discloses hydrotreating in the presence of a fatty acid salt of a VI-B metal, typically molybdenum octoate.
U.S. Pat. No. 4,077,867 discloses hydroconversion of coal in the presence of oil-soluble compound of V-B, VI-B, VII-B, or VIII metal plus hydrogen donor solvent.
U.S. Pat. No. 4,067,799 discloses hydroconversion in the presence of a metal phthalocyanine plus dispersed iron particles.
U.S. Pat. No. 4,066,530 discloses hydroconversion in the presence of (i) an iron component and (ii) a catalytically active other metal component prepared by dissolving an oil-soluble metal compound in the oil and converting the metal compound in the oil to the corresponding catalytically active metal component.
The above-noted U.S. patent application Ser. No. 07/694,591 teaches that under the conditions of operation disclosed therein, such as in Examples II-IV* and related Table II in particular, it is possible to attain improvements in, for example, conversion and other factors, by adding 10-200 wppm oil-soluble catalyst to the heterogeneous catalyst. In particular, Example I shows that it is possible to attain much higher conversion when using 160 wppm of molybdenum additive.